CN106068254A - The manufacture method of dicyanobenzenes and manufacture device - Google Patents

The manufacture method of dicyanobenzenes and manufacture device Download PDF

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CN106068254A
CN106068254A CN201580012572.4A CN201580012572A CN106068254A CN 106068254 A CN106068254 A CN 106068254A CN 201580012572 A CN201580012572 A CN 201580012572A CN 106068254 A CN106068254 A CN 106068254A
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dicyanobenzenes
liquid
organic facies
salt
absorbing liquid
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CN106068254B (en
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井比幸也
熊野达之
脇田菜摘
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/0082—Regulation; Control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0208—Separation of non-miscible liquids by sedimentation
    • B01D17/0214—Separation of non-miscible liquids by sedimentation with removal of one of the phases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1418—Recovery of products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053—Other nitrogen compounds

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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

It is an object of the invention to, when dimethylbenzene being carried out ammoxidation and manufacturing dicyanobenzenes, prevent the rotten of dicyanobenzenes and loss, manufacture dicyanobenzenes industrial and economical advantages.The manufacture method of the dicyanobenzenes of the present invention is as follows: make ammoxidation reaction gas and the organic solvent exposure of dimethylbenzene, obtain dicyanobenzenes absorbing liquid, dicyanobenzenes absorbing liquid is made to contact with the alkaline aqueous solution comprising the salt such as ammonium carbonate, to be extracted to aqueous phase by the water soluble salt neutralizing reaction generation of the carboxylic acid in dicyanobenzenes absorbing liquid and the alkali in alkaline aqueous solution, the mixed liquor of dicyanobenzenes absorbing liquid and alkaline aqueous solution is separated into organic facies and aqueous phase, the salt of ammonium carbonate tower contained in organic facies is decomposed, salt is separated from organic facies, organic facies is distilled, by low-boiling compound isolated dicyanobenzenes from organic facies contained in organic facies.

Description

The manufacture method of dicyanobenzenes and manufacture device
Technical field
The present invention relates to that dimethylbenzene is carried out ammoxidation and manufacture method and the system of use in this manufacture method of dicyanobenzenes Manufacturing apparatus.
Background technology
Dicyanobenzenes is useful compound as the raw material of pesticide, polyamide, the intermediate raw material of firming agent.Dicyan Base benzene can be by carrying out the known method system of ammoxidation by dimethylbenzene (o-Dimethylbenzene, meta-xylene and xylol) Make, for example, it is possible to utilize the method manufacture described in patent documentation 1～5.And then, known by gained dicyanobenzenes is utilized Hydrogenation hydrogenate, such that it is able to manufacture at resin curing agent, nylon, polyurethane, rubber chemicals, paper conversion agent and fibre Benzene dimethylamine useful in the industrial circle of the dimension wide scope of inorganic agent.
During it is known that use hydrogenation catalyst that dicyanobenzenes hydrogenation is manufactured benzene dimethylamine, if used by specifying The dicyanobenzenes that obtains of method, then the life-span of hydrogenation catalyst elongated (with reference to patent documentation 6).In the method for this regulation, first First, make ammoxidation reaction gas and the organic solvent exposure of dimethylbenzene, make dicyanobenzenes be dissolved in organic solvent and obtain dicyan Base benzene absorbing liquid.Then, make this dicyanobenzenes absorbing liquid contact with alkaline aqueous solution, and then liquid-liquid separation is organic facies and water Phase, removes aqueous phase.Afterwards, organic facies is distilled, will divide from organic facies by lower boiling compound compared with dicyanobenzenes From, obtain dicyanobenzenes.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 1-275551 publication
Patent documentation 2: Japanese Unexamined Patent Publication 5-170724 publication
Patent documentation 3: Japanese Unexamined Patent Publication 9-71561 publication
Patent documentation 4: Japanese Unexamined Patent Publication 11-246506 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2003-267942 publication
Patent documentation 6: International Publication the 2012/105498th
Summary of the invention
The problem that invention is to be solved
For the dicyanobenzenes obtained by the method described in patent documentation 6, owing to the content of carboxylic acid is few, therefore it is difficult to make The activity deterioration of heterogeneous system metallic catalyst, it may be said that need these catalyst when being and synthesize comprises each of benzene dimethylamine Plant the useful raw material of derivant.
But, using more than a kind comprised in the group selecting free ammonium carbonate, ammonium hydrogen carbonate and aminoquinoxaline composition In the case of obtaining such dicyanobenzenes under the industrial condition of the alkaline aqueous solution of salt, there is following problem.That is, liquid-liquid is divided Organic facies after from is dissolved with in alkaline aqueous solution the above-mentioned salt of the contained amount that cannot ignore.The salt promotion liquid of this dissolving- Operation after liquid separation is generated cyanobenzamide by dicyanobenzenes and water.Its result, dicyanobenzenes can lose.
The present invention makes in view of the foregoing, it is an object of the invention to, it is provided that: dimethylbenzene is carried out ammoxidation When manufacturing dicyanobenzenes, prevent the rotten of dicyanobenzenes and loss, industrial and economical advantages manufacture dicyanobenzenes, two The manufacture method of cyano group benzene and manufacture device.
For solving the scheme of problem
The present inventor etc., in order to reach above-mentioned purpose, conduct in-depth research, found that: use and comprise the free carbonic acid of choosing The alkaline aqueous solution of the salt of more than a kind in the group of ammonium, ammonium hydrogen carbonate and aminoquinoxaline composition is as the system of alkaline aqueous solution Make in method, have and above-mentioned salt contained in the organic facies of the operation of regulation is decomposed the operation separated in gaseous form And other various operations, such that it is able to solve above-mentioned problem.
That is, the present invention is the most following.
[1] manufacture method of a kind of dicyanobenzenes, it possesses following operation: (1) absorbs operation, makes the ammoxidation of dimethylbenzene Reacting gas and organic solvent exposure, make dicyanobenzenes be dissolved in aforementioned organic solvents and obtain dicyanobenzenes absorbing liquid, described The ammoxidation reaction gas of dimethylbenzene contains the dicyanobenzenes making dimethylbenzene carry out ammoxidation and to obtain；(2) abstraction process, before making State dicyanobenzenes absorbing liquid and more than a kind comprised in the group selecting free ammonium carbonate, ammonium hydrogen carbonate and aminoquinoxaline composition The alkaline aqueous solution contact of salt, by the neutralization by the carboxylic acid in aforementioned dicyanobenzenes absorbing liquid and the alkali in aforementioned base aqueous solution The water soluble salt that reaction generates is extracted to aqueous phase；(3) liquid-liquid separation operation, makes the aforementioned dicyan through aforementioned abstraction process The mixed liquor of base benzene absorbing liquid and aforementioned base aqueous solution is separated into organic facies and aqueous phase；(4) degassing process, will be through aforementioned In the group of the free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline composition contained in the aforementioned organic facies of liquid-liquid separation operation More than a kind salt decompose, aforementioned salt is separated from aforementioned organic facies；With, (5) low boiling separation circuit, will be through aforementioned de- The aforementioned organic facies distillation of gas operation, by the composition with the boiling point lower than aforementioned dicyanobenzenes contained in aforementioned organic facies Separate from aforementioned organic facies, obtain aforementioned dicyanobenzenes.
[2] according to manufacture method described in [1], wherein, the pressure of the gas phase in aforementioned degassing process be 101.3kPa with Under.
[3] according to manufacture method described in [1] or [2], wherein, the temperature of the liquid phase in aforementioned degassing process be 70～ 180℃。
[4] according to the manufacture method according to any one of [1]～[3], wherein, in aforementioned abstraction process, aforementioned bases is phase Ammonia for the molal quantity that total mole number is 1～50 times of aforementioned carboxylic acid contained in aforementioned dicyanobenzenes absorbing liquid.
[5] according to the manufacture method according to any one of [1]～[4], wherein, in aforementioned abstraction process, aforementioned base is made Aqueous solution and aforementioned dicyanobenzenes absorbing liquid contact under the temperature conditions below 140 DEG C.
[6] according to the manufacture method according to any one of [1]～[5], wherein, aforementioned dimethylbenzene is meta-xylene, aforementioned Dicyanobenzenes is m-dicyanobenzene.
[7] according to the manufacture method according to any one of [1]～[6], wherein, the catalysis used in aforementioned ammoxidation reaction Agent is the catalyst containing vanadium and/or chromium.
[8] according to the manufacture method according to any one of [1]～[7], wherein, prior absorbent operation absorbs aforementioned dicyan The aforementioned organic solvents of base benzene is for selecting free alkylbenzene, heterocyclic compound, aromatic nitrile compound and heterocyclic nitrile compounds composition Group in the organic solvent of more than a kind.
[9] a kind of by the dicyanobenzenes manufacture benzene dimethylamine obtained by the manufacture method according to any one of [1]～[8] Method, it possesses following hydrogenation process: make aforementioned dicyanobenzenes be dissolved in solvent, the most in the presence of a catalyst, at liquid Hydrogenate in mutually.
[10] the manufacture device of a kind of dicyanobenzenes, it possesses such as lower unit: (1) absorptive unit, makes the ammonia oxygen of dimethylbenzene Change reacting gas and organic solvent exposure, make dicyanobenzenes be dissolved in aforementioned organic solvents and obtain dicyanobenzenes absorbing liquid, institute The ammoxidation reaction gas stating dimethylbenzene contains the dicyanobenzenes making dimethylbenzene carry out ammoxidation and to obtain；(2) extraction unit, makes Aforementioned dicyanobenzenes absorbing liquid and more than a kind comprised in the group selecting free ammonium carbonate, ammonium hydrogen carbonate and aminoquinoxaline composition Salt alkaline aqueous solution contact, by by the carboxylic acid in aforementioned dicyanobenzenes absorbing liquid and the alkali in aforementioned base aqueous solution The water soluble salt generated with reaction is extracted to aqueous phase；(3) liquid-liquid separation unit, make from aforementioned extraction unit send aforementioned The mixed liquor of dicyanobenzenes absorbing liquid and aforementioned base aqueous solution is separated into organic facies and aqueous phase；(4) degassing unit, will be from aforementioned The free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline composition contained in the aforementioned organic facies that liquid-liquid separation unit is sent The salt of more than a kind in group decomposes, and aforementioned salt is separated from aforementioned organic facies；With, (5) low boiling separative element, will be from aforementioned The aforementioned organic facies distillation that degassing unit is sent, has the boiling point lower than aforementioned dicyanobenzenes by contained in aforementioned organic facies Composition separate from aforementioned organic facies, obtain aforementioned dicyanobenzenes.
The effect of invention
According to the present invention, when dimethylbenzene is carried out ammoxidation manufacture dicyanobenzenes, it is provided that be prevented from dicyanobenzenes Rotten and loss, industrial and economical advantages ground manufactures dicyanobenzenes, the manufacture method of dicyanobenzenes and manufacture device.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the example manufacturing device used in the manufacture method of the dicyanobenzenes illustrating the present invention.
Detailed description of the invention
Hereinafter, the most referring to the drawings, the mode implementing the present invention (below, is referred to simply as " this embodiment party simultaneously Formula ") it is described in detail, but the present invention is not limited to following present embodiment.The present invention can be at the model without departing from its purport Various deformation is carried out in enclosing.It should be noted that in accompanying drawing, same key element is marked same symbol, omit repeat specification.Separately Outward, position relationship such as grade is as long as no being particularly limited to up and down, based on position relationship shown in the drawings.And then, the size of accompanying drawing Ratio is not limited to the ratio of diagram.
(manufacture method of dicyanobenzenes)
The manufacture method of the dicyanobenzenes of present embodiment possesses following operation: (1) absorbs operation, makes the ammonia oxygen of dimethylbenzene Change reacting gas and organic solvent exposure, make dicyanobenzenes be dissolved in above-mentioned organic solvent and obtain dicyanobenzenes absorbing liquid, institute The ammoxidation reaction gas stating dimethylbenzene contains the dicyanobenzenes making dimethylbenzene carry out ammoxidation and to obtain；(2) abstraction process, makes Above-mentioned dicyanobenzenes absorbing liquid and more than a kind comprised in the group selecting free ammonium carbonate, ammonium hydrogen carbonate and aminoquinoxaline composition Salt alkaline aqueous solution contact, by by the carboxylic acid in above-mentioned dicyanobenzenes absorbing liquid and the alkali in above-mentioned alkaline aqueous solution The water soluble salt generated with reaction is extracted to aqueous phase；(3) liquid-liquid separation operation, makes the dicyanobenzenes through this abstraction process The mixed liquor of absorbing liquid and above-mentioned alkaline aqueous solution is separated into organic facies and aqueous phase；(4) degassing process, will divide through this liquid-liquid In the group of the free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline composition contained in the organic facies of operation more than a kind Salt decomposes, and separates from aforementioned organic facies；With, (5) low boiling separation circuit, steams the above-mentioned organic facies through this degassing process Evaporate, the composition with the boiling point lower than dicyanobenzenes contained in this organic facies is separated from organic facies, obtains dicyano Benzene.
" dicyanobenzenes " in the present invention refers to, phthalonitrile (i.e. 1,2-dicyanobenzenes), m-dicyanobenzene (i.e. 1,3-bis- Cyano group benzene) or para-Phthalonitrile (i.e. Isosorbide-5-Nitrae-dicyanobenzenes), respectively by corresponding dimethylbenzene i.e. o-Dimethylbenzene, meta-xylene or right Dimethylbenzene is manufactured by known method for ammoxidation.
(1) operation is absorbed
Absorb in operation, make ammoxidation reaction gas and the organic solvent exposure of dimethylbenzene, the ammoxidation of described dimethylbenzene Reacting gas contains the dicyanobenzenes making dimethylbenzene carry out ammoxidation and to obtain, and makes dicyanobenzenes be absorbed in organic solvent.
Ammoxidation reaction can utilize known method to carry out.For example, it is possible to make to be mixed with the reaction of dimethylbenzene, oxygen and ammonia Unstrpped gas contacts with the catalyst of ammoxidation reaction, carries out ammonia reaction under the conditions of described later.Urging in ammoxidation reaction The form changing bed can be fluid bed or fixed bed,.Catalyst as ammoxidation, it is possible to use known catalyst, The such as catalyst described in patent documentation 1,2,4 or 5, wherein, more preferably containing vanadium and/or the catalyst of chromium.Ammoxidation The quantity delivered of the ammonia used in reaction is preferably the model of 2～20 moles, more preferably 6～15 moles relative to dimethylbenzene 1 mole Enclose.When the quantity delivered of ammonia is in above-mentioned scope, the yield of dicyanobenzenes becomes better, and space-time yield improves the most further.Logical Cross contained by the gas of ammoxidation reaction generation and the mixture i.e. ammoxidation reaction gas of unreacted reaction raw materials gas Unreacted ammonia can reclaim and be re-used for ammoxidation reaction.The quantity delivered of the oxygen used in ammoxidation reaction is relative to dimethylbenzene 1 mole of scope being preferably more than 3 moles, more preferably 3～100 moles, more preferably 4～100 moles.The supply of oxygen Amount is for time in above-mentioned scope, and the yield of dicyanobenzenes becomes better, and space-time yield improves the most further.Supply as oxygen Source, it is possible to use air.
The reaction temperature of ammoxidation is preferably the scope of 300～500 DEG C, more preferably 330～470 DEG C.Reaction temperature is Time in above-mentioned scope, the conversion ratio of dimethylbenzene becomes better, and the generation of carbon dioxide and Blausure (German) etc. is suppressed, permissible Dicyanobenzenes is manufactured with better yield.The reaction pressure of ammoxidation can be normal pressure, pressurization (i.e. higher than the pressure of normal pressure) Or decompression (i.e. less than the pressure of normal pressure), from the viewpoint of as reaction temperature, preferably normal pressure (atmospheric pressure: example Such as 100kPa)～the scope of 300kPa.It addition, space velocity (the Gas Hourly Space of the reaction raw materials in ammoxidation Velocity=GHSV) 500～5000h it are preferably-1。
Absorbing in operation, " making dicyanobenzenes be absorbed in organic solvent " refers to, makes the dicyano in ammoxidation reaction gas Benzene is dissolved in organic solvent.As the organic solvent used in the absorption of dicyanobenzenes, it can be the boiling point than dicyanobenzenes Dissolubility low, dicyanobenzenes is higher and be inactive organic solvent to dicyanobenzenes.As meeting the organic of these conditions Solvent, such as, can enumerate: the alkane such as dimethylbenzene (adjacent body, mesosome, to body), 1，2，4-trimethylbenzene, sym-trimethylbenzene. and ethylo benzene Base benzene；The heterocyclic compounds such as picoline；The aromatic nitrile compounds such as methyl cyanophenyl (adjacent body, mesosome, to body) and benzonitrile；And cyanogen The heterocyclic nitrile compounds such as yl pyridines, the organic solvent of more than a kind be preferably selected from the group being made up of them.Wherein, from In ammoxidation reaction from the viewpoint of by-product, particularly preferred methyl cyanophenyl.
Absorb in operation, from the viewpoint of more effectively and positively absorbing dicyanobenzenes, preferably make ammoxidation reaction gas Body and the organic solvent exposure of 80～200 DEG C, preferably with organic solvent exposure 1～30 seconds, more preferably to meet the two condition Mode make organic solvent exposure.From the viewpoint of more effectively and positively absorbing dicyanobenzenes, absorb in operation is organic The consumption of solvent is preferably 0.5～20 mass parts relative to dicyanobenzenes 1 mass parts.In order to make organic solvent and ammoxidation reaction Gas contacts, it is possible to use gas-liquid contact apparatus etc..Organic solvent and the flowing of ammoxidation reaction gas in this device are permissible For convection type and parallel type,.It addition, such as, in the bottom of the container of storage organic solvent, gas mouth blown is set, from this Ammoxidation reaction gas is sent in organic solvent by gas mouth blown, thus both can also be made to contact.
(2) abstraction process
In abstraction process, the dicyanobenzenes absorbing liquid obtained through absorbing operation is made to contact with alkaline aqueous solution, will be by two The water soluble salt neutralizing reaction generation of the carboxylic acid in cyano group benzene absorbing liquid and the alkali in alkaline aqueous solution is extracted to aqueous phase.This The so-called carboxylic acid in place, refers to the material by ammoxidation reaction by-product, such as, can enumerate: cyanobenzoic acid is (adjacent body, mesosome, right Body), ar-Toluic acid (adjacent body, mesosome, to body) and phthalic acid (neighbour's body, mesosome, to body).
Dicyanobenzenes absorbing liquid is made to contact with alkaline aqueous solution more well for efficiency, it is possible to use have blender Mixing channel, it is possible to use the cast mixers such as static mixer.It addition, be particularly required for the device for mixing, can Think and make alkaline aqueous solution mix with the jet flow at the flowing interflow of dicyanobenzenes absorbing liquid.The mode of the extraction in abstraction process can Think batch (-type), semibatch and continuous way,.
Alkali contained in alkaline aqueous solution is not particularly limited, and can be inorganic base and organic base,.As such Alkali, such as, can enumerate: ammonia, sodium hydroxide and potassium hydroxide.Wherein, from by the neutralization with the carboxylic acid dicyanobenzenes absorbing liquid The salt that reaction generates is necessary for water soluble, can obtain at a low price and can be with efficiency more well by dicyanobenzenes absorbing liquid Carboxylic acid neutralize aspect set out, preferably ammonia.
The consumption of alkali (such as ammonia) can be contained with dicyanobenzenes absorbing liquid with molar basis amount total of carboxylic acid It is calculated as more than equal.Specifically, the consumption of alkali is preferred relative to the total mole number of carboxylic acid contained in dicyanobenzenes absorbing liquid It is the molal quantity of 1～50 times, more preferably 2～30 times, more preferably 3～15 times.The concentration of the ammonia in alkaline aqueous solution Suitably can adjust according to the amount of carboxylic acid contained in dicyanobenzenes absorbing liquid.Specifically, the ammonia in alkaline aqueous solution is dense Degree is preferably 0.1～20 mass %, more preferably 0.1～10 mass %
Alkaline aqueous solution is not particularly limited relative to the consumption of dicyanobenzenes absorbing liquid, in terms of quality criteria, industrial Expect that with dicyanobenzenes absorbing liquid be below equivalent.Specifically, when using ammonia spirit as alkaline aqueous solution, its consumption is excellent Elect 1～100 mass % of dicyanobenzenes absorbing liquid, more preferably 2～50 mass %, more preferably 5～30 mass % as. Part or all of alkaline aqueous solution can use the aqueous phase reclaimed in the liquid-liquid separation operation of next operation.Under consideration The liquid-liquid separation operation of one operation, it is desirable to contain the free ammonium carbonate of choosing, ammonium hydrogen carbonate and amino first in alkaline aqueous solution in advance The salt of more than a kind in the group of acid ammonium composition.This salt is dissolved in alkaline aqueous solution and coexists with alkali and improve fluid density, from Without the extraction of carboxylic acid is had undesirable effect, the separating rate of liquid-liquid separation can be improved.It addition, this salt can be independent Use or use in any combination.Particularly, the aqueous solution being dissolved with ammonium carbonate and ammonia can be by ammonia spirit It is passed through the carbonated gas of bag inexpensively and easily to prepare.Therefore, such aqueous solution is industrial useful extraction Agent, for industrial preferred alkaline aqueous solution.The consumption of this salt can be fitted according to the separating rate required in liquid-liquid separation operation Work as adjustment.Generally, this salt meltage in alkaline aqueous solution is 1～30 mass % relative to alkaline aqueous solution.
Temperature (following, to be referred to as " Contact Temperature " in this operation) when making dicyanobenzenes absorbing liquid contact with alkaline aqueous solution It is preferably 70 DEG C～140 DEG C, more preferably 70 DEG C～120 DEG C, more preferably 70 DEG C～110 DEG C.By by Contact Temperature It is set to less than 140 DEG C, is possible to prevent to be generated in a large number by dicyanobenzenes cyanobenzamide, cyanobenzoic acid and benzenedicarboxamide, It is possible to prevent the dicyanobenzenes dissolving to aqueous phase, prevents the loss of dicyanobenzenes, therefore preferably.On the other hand, under Contact Temperature As long as limit is the temperature that in dicyanobenzenes absorbing liquid, dicyanobenzenes can keep dissolved state.Such as, in m-tolunitrile In the case of absorption has the solution that m-dicyanobenzene concentration is 10 mass % of m-dicyanobenzene, by Contact Temperature being controlled at 70 DEG C Above liquid temperature, is possible to prevent the precipitation of m-dicyanobenzene, therefore preferably.
In order to reduce wastewater flow rate, can be using the aqueous phase of recovery in the liquid-liquid separation operation of next operation as aforementioned bases Property aqueous solution part or all use.Wherein it is possible to add organic solvent in the aqueous phase of this recovery to form emulsion, make this Emulsion contacts with dicyanobenzenes absorbing liquid.As the organic solvent added in the case of this, such as, can enumerate: dimethylbenzene (adjacent body, Mesosome, to body), 1,2,4-trimethylbenzene, the alkylbenzene such as sym-trimethylbenzene. and ethylo benzene；The heterocyclic compounds such as picoline；Methyl The aromatic nitrile compounds such as cyanophenyl (adjacent body, mesosome, to body) and benzonitrile；With the heterocyclic nitrile compounds such as cyanopyridine, from emulsion shape From the viewpoint of one-tenth, the organic solvent of more than a kind be preferably selected from the group being made up of them.And then, particularly preferably will absorb The organic solvent used in operation is for the preparation of emulsion.
Pressure (following, to be referred to as " contact pressure " in this operation) when making dicyanobenzenes absorbing liquid contact with alkaline aqueous solution Atmospheric pressure～pressurized state can be suitably adjusted to according to temperature conditions.As long as contact pressure keeps liquid for dicyanobenzenes absorbing liquid At least one holding liquid phase of phase and alkaline aqueous solution and the desired amount of alkali is present in as aqueous phase with the neutralization of carboxylic acid Pressure.Alternatively, it is also possible to as required, the non-active gas such as nitrogen, argon is made to coexist.As contained in alkaline aqueous solution Salt, in the case of individually or in any combination using ammonium carbonate, ammonium hydrogen carbonate and aminoquinoxaline, if Contact Temperature is Within 140 DEG C, then contact pressure suitably can adjust in the scope of below 1.6MPaG.
From the viewpoint of the loss of suppression dicyanobenzenes, needed for the contacting of dicyanobenzenes absorbing liquid and alkaline aqueous solution Within time is preferably 2 hours, within more preferably 1 hour, more preferably within 30 minutes.Also depend on and make dicyano The method that benzene absorbing liquid contacts with alkaline aqueous solution, usually several seconds～30 minutes.
By the salt that water soluble salt is above-mentioned carboxylic acid and above-mentioned alkali generated in abstraction process aqueous phase, such as, can lift Go out: cyanobenzoic acid ammonium, ar-Toluic acid ammonium and phthalic acid ammonium.
(3) liquid-liquid separation operation
In liquid-liquid separation operation, make to divide through the dicyanobenzenes absorbing liquid of abstraction process and the mixed liquor of alkaline aqueous solution From for organic facies and aqueous phase.That is, it is separated as organic facies and aqueous phase.As separation method, can be to stand mixed liquor to make it The method carrying out being separated.It addition, in addition, as separation method, can be centrifugal separator, coalescer and separator The known method such as it is applied in combination.Temperature and pressure condition during liquid-liquid separation is not particularly limited, as long as being can be by these The condition being separated, it is desirable to for being equal extent with the condition of abstraction process.If temperature during liquid-liquid separation, pressure from Temperature, pressure in abstraction process are greatly reduced, then the dicyanobenzenes being dissolved in aqueous phase separates out trace, becomes pipe arrangement obstruction etc. Reason, moreover, aqueous phase becomes no longer to keep liquid phase state to be difficult to separate.
(4) degassing process
In degassing process, by selected from ammonium carbonate, ammonium hydrogen carbonate and ammonia contained in the organic facies of liquid-liquid separation operation The salt of more than a kind in base ammonium formate decomposes, and is separated by this salt from organic facies.Now, salt separates in gaseous form.
In organic facies separated from the water in liquid-liquid separation operation, the alkaline aqueous solution used in abstraction process is molten with it The degree of Xie Du and exist.Therefore, in the past, the salt being dissolved in organic facies is particularly in steaming to back segment after liquid-liquid separation Promote in the range of till evaporating process to be generated cyanobenzamide by dicyanobenzenes and water, make dicyanobenzenes lose.Thus, organic Xiang Zhongyue comprises salt in a large number, and the loss amount of dicyanobenzenes becomes the biggest.On the other hand, it is desirable to salt and the tool of organic facies will be dissolved in When the composition (hereinafter also referred to as " low-boiling compound ") having the boiling point lower than dicyanobenzenes separates together from organic facies, The temperature of organic facies uprises, and the rotten of dicyanobenzenes is easily carried out further, and accordingly, as result, dicyanobenzenes is easier to damage Lose.But, in present embodiment, salt contained in organic facies is decomposed in this degassing process and separates thus reduce, therefore, The loss of dicyanobenzenes is suppressed.Due in the organic facies after separated salt in this operation by low in following low boiling separation circuit Boiling-point compound separates, therefore, even if improving the temperature of organic facies, the change that can also suppress dicyanobenzenes compared with the past Matter.And then, in this degassing process, the reduction with the salt in organic facies simultaneously can also reduce the water in organic facies.By with The water of the reaction of formation raw material as cyanobenzamide is reduced by dicyanobenzenes together, such that it is able to suppress dicyano further The loss of benzene.
In the group of the free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline composition contained in organic facies more than a kind Under the conditions of salt makes organic facies be in the pressure and temperature of regulation in this operation, such that it is able to be decomposed into carbon dioxide and ammonia, with The form of gas is removed.On the other hand, the pressure and temperature in this operation is preferably according to other compositions in organic facies the most not The carbon dioxide and the adjoint mode of ammonia that generate after decomposing with salt in gaseous form set.Specifically, gas phase is (in this operation Be its tower top when using degassing tower) pressure expectation subtract with the carbanion in the organic facies extracted out and the content of ammonium radical ion The most extremely mode with the temperature that content is equal extent of each ion in the dicyanobenzenes absorbing liquid absorbed in operation sets.More Specifically, the pressure of gas phase can be atmospheric pressure (101.3kPa), it is also possible to under reduced pressure (less than 101.3kPa), excellent Elect 101.3kPa as, more preferably below 70kPa, more preferably below 50kPa.From the damage suppressing dicyanobenzenes further Lose and more reliably decompose and separated salt and then organic facies keep the dissolved state of dicyanobenzenes, further suppression it goes bad From the viewpoint of, the pressure of gas phase is preferably 10kPa～101.3kPa, more preferably 10kPa～70kPa, more preferably 10kPa～50kPa.
It addition, from the viewpoint of as pressure, the temperature of liquid phase (being at the bottom of its tower during use degassing tower in this operation) It is preferably 70～180 DEG C, more preferably 90～160 DEG C, more preferably 100～140 DEG C.Such as, organic facies is by isophthalic In the case of the solution that m-dicyanobenzene concentration is 10 mass % that dintrile m-tolunitrile absorbs and obtains, the temperature of liquid phase is excellent Elect more than 70 DEG C as.
By pressure and temperature is set to above-mentioned under the conditions of, carbanion and the ammonium radical ion of main composition salt are more effective Ground decomposes.Its result, the content of the above-mentioned each ion in organic facies can be sufficiently reduced to and the dicyanobenzenes absorbing in operation The content of the above-mentioned each ion in absorbing liquid is equal extent.By the reduction of this salt, the rotten damage caused of dicyanobenzenes Lose and be suppressed.
Salt by more than a kind in the group of the free ammonium carbonate of choosing in organic facies, ammonium hydrogen carbonate and aminoquinoxaline composition As long as organic facies can be set as above-mentioned pressure and temperature by the device used in the method decomposed and separate, it can be tower Can also be tank (groove), be not particularly limited.Such as, in this operation, use tower (degassing tower) to be decomposed by salt, divide from organic facies In the case of from, the carbon dioxide generated from tower top discharge salt decomposition and ammonia, water and organic solvent.On the other hand, from tower Part or all of organic facies being decomposed and removing of salt is extracted at the end out.The water can discharged from tower top and organic solvent are by cold Condensers etc. reclaim, and then are separated with organic solvent by water, and organic solvent is back to this degassing tower.Through the water and organic reclaimed In the case of solvent is difficult to separate, can not separate water into and directly water and organic solvent are back to this degassing tower, at back segment Low boiling separation circuit in water separated with organic facies and removes.
The temperature of the organic facies of the unit feeding used in these operations such as degassing tower is previously heated to before being expected to supply The temperature that column bottom temperature is equal extent with degassing tower.
In degassing process, the device arranged in series used in method salt can decomposed and separate, in each device, will Salt decomposes and separates from organic facies.In the case of above-mentioned, in front end devices, will decompose and the part of separated salt and having of obtaining Machine supplies mutually to rear section apparatus, in this rear section apparatus, is decomposed the organic facies with separated salt further.
For the manufacture method of the dicyanobenzenes of present embodiment, can will conventional described later low boiling separation circuit make Device in the salt brought into and water remove from organic facies in advance in degassing process, therefore, it can reduce low boiling and separate work Operating load in sequence, separates required temperature, the load of pressure for example, it is possible to reduce by salt, water with dicyanobenzenes.
(5) low boiling separation circuit
In low boiling separation circuit, the organic facies through degassing process is distilled, by low boiling chemical combination contained in organic facies Thing separates from organic facies, obtains dicyanobenzenes.In this operation, by part or all of low-boiling compound from organic facies Separate.It addition, in this operation, dicyanobenzenes obtains with the state of liquid, and low-boiling compound separates with the state of gas.Enter And, low-boiling compound also comprises organic solvent.As long as the distillating method in this operation can be by low-boiling compound from having Machine middle removal (i.e., it is possible to separated with dicyanobenzenes by low-boiling compound) mutually is just not particularly limited.Thus, distillating method can Think any distillating method in batch (-type) and continuous way.Such as, when this operation using distillation column distill, comprise The low-boiling compound of organic solvent can only be discharged from tower top, can be from tower top and side-draw portion (concentrating part；Supply with raw material Comparing near top to portion) both discharge.It addition, the low-boiling compound discharged is reclaimed, as required, it is separated into organic molten Agent and other low-boiling compounds, then using the low-boiling compound comprising organic solvent or organic solvent as absorbing operation In the organic solvent of dicyanobenzenes contained in the absorbing ammonia oxidation reaction gas use.And then, organic the lowest in order to make The supply flow rate of the devices such as the distillation column that in boiling separation circuit, distillation is used is stable, by temporary transient for the organic facies through degassing process It is stored in tank etc., is then supplied in low boiling separation circuit the device used.
The pressure of the distillation in this operation is preferably under decompression, more preferably with gas phase side (as tower top during use distillation column) Pressure is calculated as 1～30kPa.If the scope of above-mentioned pressure, then can more effectively and positively suppress the rotten of dicyanobenzenes. It addition, the temperature of distillation is preferably the temperature that dicyanobenzenes does not separates out, such as, when using distillation column, preferably concentrating part is (with former Material supply unit is compared near top) in the temperature that do not separates out of dicyanobenzenes.Use distillation column time, from the bottom of the tower of distillation column with liquid (molten state) obtains dicyanobenzenes.
The supplying temperature of device (such as distillation column) used in organic distillation in opposite directions can be with its just before work The temperature of the liquid phase in sequence is equal extent.It addition, the temperature for the liquid phase of the device used in distillation (is tower during distillation column End temperature), in order to suppress to heat the generation of the dicyanobenzenes polymer group caused, preferably more than the fusing point of dicyanobenzenes Temperature and be set to low temperature as far as possible.Specifically, for the temperature of liquid phase, when dicyanobenzenes is phthalonitrile, preferably 150～ 200 DEG C, more preferably 150～180 DEG C, more preferably 150～170 DEG C.When dicyanobenzenes is m-dicyanobenzene, the temperature of liquid phase Degree is preferably 170～220 DEG C, more preferably 170～200 DEG C, more preferably 170～190 DEG C.Dicyanobenzenes is to benzene two During formonitrile HCN, the temperature of liquid phase is preferably 240～290 DEG C, more preferably 240～270 DEG C, more preferably 240～260 DEG C. It addition, in liquid phase (being at the bottom of tower during distillation column), in order to suppress the generation of dicyanobenzenes polymer group, the dicyano of preferred molten state The holdup time of benzene is short, such as, within the holdup time of dicyanobenzenes is preferably 180 minutes, and more preferably 10～120 minutes, More preferably 15～60 minutes, particularly preferably 20～30 minutes.From the same viewpoint, during design distillation column, excellent Volume at the bottom of tower is set to the least in the range of the operating not hindering distillation column by choosing.
In low boiling separation circuit, can will be separated the device string used in low-boiling compound from organic facies by distillation Townhouse arranges, and in each device, separates low-boiling compound by distillation from organic facies.In the case of above-mentioned, in the device of leading portion, The organic facies comprising a dicyanobenzenes part for low-boiling compound being isolated by distillation is supplied to back segment Device, in the device of this back segment, is separated part or all of low-boiling compound by distillation further, is comprised The organic facies of dicyanobenzenes.
By the dicyanobenzenes obtained by the manufacture method of present embodiment, through the hydrogenation process of the following stated, thus Benzene dimethylamine can be manufactured.Herein, " benzene dimethylamine " refers to, O-phthalic amine, m-xylene diamine or p dimethylamine, will be respectively Corresponding phthalonitrile (i.e. 1,2-dicyanobenzenes), m-dicyanobenzene (i.e. 1,3-dicyanobenzenes) or para-Phthalonitrile (i.e. 1,4- Dicyanobenzenes) carry out hydrogenating such that it is able to manufacture.
(6) hydrogenation process
In hydrogenation process, the dicyanobenzenes of the molten state through too low boiling separation circuit is made to be dissolved in solvent, then in catalysis In the presence of agent, hydrogenate in the liquid phase.As solvent, such as, can enumerate: liquid ammonia, benzene dimethylamine are mixed with liquid ammonia Bonding solvent, aromatic hydrocarbon (such as, dimethylbenzene, sym-trimethylbenzene. and pseudocumene etc.) and the mixed solvent of liquid ammonia, benzene dimethylamine Mixed solvent with aromatic hydrocarbon Yu liquid ammonia.
Liquid ammonia concentration in solvent is the highest, more can improve the yield of the benzene dimethylamine utilizing hydrogenation, therefore, excellent Select the liquid ammonia concentration height person in solvent, more than the most preferably 60 mass %, particularly preferably 100 mass %.
Quantity of solvent during hydrogenation is preferably 1～99 mass parts relative to dicyanobenzenes 1 mass parts, more preferably 3～ 99 mass parts, more preferably 5～99 mass parts.When quantity of solvent is in above-mentioned scope, solvent can be reduced further and return Energy needed for receipts, is both economically advantageous, furthermore it is possible to the selection rate of the benzene dimethylamine improved further in hydrogenation.
The dicyanobenzenes making molten state is dissolved in the operation of solvent and the cast mixers such as static mixer can also be used Carry out.Wherein, when using cast mixer, there is the probability of mixer internal congestion due to the attachment of insoluble component that separates out. From the viewpoint of preventing such phenomenon, preferably in dissolving tank, dicyanobenzenes mixed with solvent and make it dissolve.Pass through In dissolving tank, supply dicyanobenzenes and the solvent of molten state, thus need not stir especially and it just can be made to dissolve, but basis Needs can also be stirred.Pressure and temperature in dissolving tank keeps liquid phase and dicyanobenzenes to be held by solvent with solvent Diffluent mode selects.From such a viewpoint, specifically, the pressure in dissolving tank is preferably 0.5～15MPa, more It is preferably 0.7～10MPa, more preferably 1～8MPa.From the same viewpoint, the solution temperature in dissolving tank is preferred It is 3～140 DEG C, more preferably 5～120 DEG C, more preferably 10～100 DEG C.
When solution produces insoluble component, can by one part or all supply divided by solid-liquid to hydrogenation From removing.As solid-liquid separation, it is possible to use known methods such as filtration, centrifugation and Shen fall separation.Wherein, it is preferably Filtering, the filtration simplicity especially utilizing sintered metal filter and/or coarse filter is applicable.
Hydrogen for hydrogenation can also comprise impurity, such as methane and the nitrogen etc. being not involved in reacting.Wherein, logical Cross the impurity concentration in suppression hydrogen, be easier to ensure that required hydrogen partial pressure, reduce reaction stagnation pressure further, industrial become More favourable, therefore, density of hydrogen is preferably 50 moles of more than %.
Catalyst as hydrogenation, it is possible to use known carrier band metallic catalyst, non-carrier band metallic catalyst, Ruan Inner catalyst or noble metal catalyst etc..Wherein, it is suitable for using containing nickel and/or the catalyst of cobalt.If the consumption of catalyst The consumption employed in liquid-phase hydrogenation for known dicyanobenzenes is just not particularly limited.
The form of the catalytic bed in hydrogenation can be fixed bed and suspension bed,.It addition, hydrogenation can be adopted By any means in batch (-type) and continuous way,.When the catalytic bed utilizing fixed bed carries out continuous flow reaction, can adopt By an endless form part for gained hydrogenation liquid returned continuously to hydrogenation reactor from the outlet of hydrogenation reactor. In the case of above-mentioned, can be independent in a looping fashion, or as described in Japanese Unexamined Patent Publication 2008-31155 publication, combination follows Ring mode and single-channel mode use.When utilizing batch (-type) to carry out hydrogenation, it is little that the hydrogenation time is preferably 0.5～8 Time, when utilizing continuous way to carry out hydrogenation, space velocity (the Liquid Hourly Space Velocity=of reaction raw materials LHSV) 0.1～10h it is preferably-1。
The pressure and temperature of hydrogenation selects in the way of hydrogenation is carried out and solvent keeps liquid phase.Hydrogenation Temperature be preferably 20～200 DEG C, more preferably 30～150 DEG C, more preferably 40～120 DEG C.Hydrogen in hydrogenation Atmospheric pressure is preferably 1～30MPa, more preferably 2～25MPa, and more preferably 3～20MPa.
In the hydrogenation of dicyanobenzenes, manufacture benzene dimethylamine more well for efficiency, preferably improve itrile group to amino methyl Hydrogenation carry out degree.To this end, the dicyanobenzenes preferably selected in the liquid that will obtain after hydrogenation and cyano group benzyl The concentration of base amine remains the reaction condition of low state.Specifically, by the amount of cyanobenzyls amine relative to hydrogenation after Benzene dimethylamine 100 mass % in the liquid obtained is preferably maintained at below 5.0 mass %, more preferably remains 1.0 mass % Hereinafter, below 0.2 mass % is further preferably remained.It addition, the conversion ratio of dicyanobenzenes is preferably more than 99.50%, more It is preferably more than 99.90%, more preferably more than 99.95%.Above-mentioned each reaction condition (solvent, catalyst, raw material, hydrogen Atmospheric pressure and reaction formation etc.) combination in, by suitably selecting temperature or time, this hydrogenation can be kept as described above anti- That answers carries out degree.
The benzene dimethylamine generated by hydrogenation can be by known method purification such as distillations.Want to obtain more high-purity During the benzene dimethylamine spent, the cyanobenzyls amine comprised together with benzene dimethylamine in the liquid after preferably removing hydrogenation.But, Cyanobenzyls amine is the least with the difference of the boiling point of corresponding benzene dimethylamine, utilizes common distillation to be difficult to separate.Therefore, it can Before being distilled by liquid after hydrogenation, by the method in addition to distillation, from this liquid, remove cyanobenzyls amine.Now The minimizing technology of cyanobenzyls amine be not particularly limited, such as can enumerate: by hydration reaction, cyanobenzyls amine is converted For can the method for the cyanobenzamide of separated relatively easily；And as in Japanese Unexamined Patent Publication 2007-332135 publication As record, after the liquid ammonia of hydrogenation solvent being removed, in the presence of a catalyst, cyanobenzyls amine is carried out catalytic hydrogenation And reduce the method etc. of the amount of cyanobenzyls amine.
(the manufacture device of dicyanobenzenes)
The manufacture device used in the manufacture method of the dicyanobenzenes of present embodiment possesses such as lower unit: (1) absorbs single Unit, makes ammoxidation reaction gas and the organic solvent exposure of dimethylbenzene, makes dicyanobenzenes be dissolved in organic solvent and obtain dicyan Base benzene absorbing liquid, the ammoxidation reaction gas of described dimethylbenzene contains the dicyanobenzenes making dimethylbenzene carry out ammoxidation and to obtain； (2) extraction unit, makes dicyanobenzenes absorbing liquid and comprises in the group selecting free ammonium carbonate, ammonium hydrogen carbonate and aminoquinoxaline composition The alkaline aqueous solution contact of salt of more than a kind, by by the carboxylic acid in dicyanobenzenes absorbing liquid and the alkali in alkaline aqueous solution The water soluble salt neutralizing reaction generation is extracted to aqueous phase；(3) liquid-liquid separation unit, makes the dicyano sent from extraction unit The mixed liquor of benzene absorbing liquid and alkaline aqueous solution is separated into organic facies and aqueous phase；(4) degassing unit, will be from liquid-liquid separation unit The salt of more than a kind in the group of the free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline composition contained in the organic facies sent Decompose, salt is separated from organic facies；With, (5) low boiling separative element, the organic facies distillation will sent from degassing unit, will have Machine mutually in the contained composition with the boiling point lower than dicyanobenzenes separate from organic facies, obtain dicyanobenzenes.
Fig. 1 is the signal of the example manufacturing device used in the manufacture method of the dicyanobenzenes illustrating present embodiment Figure, more specifically, for manufacturing the process chart of the device of m-dicyanobenzene by ammoxidation reaction.This manufacture device possesses: Ammonia oxidation reactor A as the unit making ammoxidation reaction carry out；Absorption tower B as above-mentioned absorptive unit；As above-mentioned Extraction unit and the mixing channel C of the part as above-mentioned liquid-liquid separation unit；As above-mentioned liquid-liquid separation unit liquid- Liquid separating tank D；Degassing tower E as above-mentioned degassing unit；Low boiling knockout tower F as above-mentioned low boiling separative element；As inciting somebody to action Dicyanobenzenes is dissolved in the dissolving tank G dissolving unit of solvent；As by the insoluble component mistake from the solution that dissolving tank G sends The filter H of the unit of filter；With, as the liquid to send from filter H as raw material, carry out the hydrogenation of dicyanobenzenes The hydrogenation reactor I of unit.
Ammonia oxidation reactor A and hydrogenation reactor I is filled with in each reaction the catalyst used.It addition, ammoxidation is anti- Answer device A, absorption tower B, mixing channel C, liquid-liquid separation groove D, degassing tower E, low boiling knockout tower F, dissolving tank G, filter H and hydrogenation It is connected on reactor I for receiving gas, the pipe arrangement of liquid and for will be at this sent from the device of its leading portion Carry out the gas after the process specified in device, liquid is sent to the pipe arrangement of device of back segment.And then, ammonia oxidation reactor A, suction Receive on tower B, mixing channel C, liquid-liquid separation groove D, degassing tower E, low boiling knockout tower F, dissolving tank G, filter H and hydrogenation reactor I It is accompanied with the heating units such as heat exchanger the most as required.It addition, each pipe arrangement be provided with the pressure for adjusting in each device, Or adjust gas, the valve of flow of liquid receiving in each device or sending from each device.And then, mixing channel C and liquid-liquid separation Groove D is different grooves in FIG but it also may use 1 groove to be used as mixing channel C and liquid-liquid separation groove D.
Additionally, the form of each device, operating condition etc. are as explanation in above-mentioned " (manufacture method of dicyanobenzenes) ", because of This, omit explanation herein.
Embodiment
Then, the present invention is specifically described according to below example.But, the present invention is not limited by these embodiments System.
The analysis of organic impurities (cyanobenzamide and cyanobenzoic acid etc.) contained in dicyanobenzenes uses liquid phase color Spectrometry, (supply is to unreacted in the material of hydrogenation for the liquid after dicyanobenzenes absorbing liquid, dicyanobenzenes or hydrogenation The material of residual and with the mixed liquor of hydrogenation reaction product) analysis use gas chromatography.It addition, respectively, in organic facies Moisture concentration be analyzed by determination of trace water device, carbon acid ion concentration is analyzed by titration, ammonium root from Sub-concentration is analyzed by electrophoretic apparatus.For salinity, convert according to carbon acid ion concentration.
(1) liquid chromatography analysis
Liquid chromatography analysis uses the LC of CAPCELL PAK C18 (trade name) manufactured equipped with Shiseido The geopressure gradient LC system of the UV-VIS detector manufactured with Shimadzu Scisakusho Ltd of post.Use acetonitrile (pure with light Medicine Industrial Co., Ltd manufactures, superfine) and the mixed liquor of 0.5 mass % phosphate aqueous solution as solvent and the phase that flows, at column temperature 35 DEG C of case, the flow velocity under conditions of 1.0mL/ minute of flowing phase, be analyzed organic impurities contained in dicyanobenzenes.
(2) gas chromatography analysis
Gas chromatography analysis uses the GC post of the DB-1 equipped with the manufacture of J&W Co., Ltd., the manufacture of Agilent company 6890 type GC analytical equipments.Setting for temperature, sample injection port is set to 230 DEG C, and detector is set to 295 DEG C.Column oven is 100 After keeping 10 minutes at DEG C, it is warming up to 280 DEG C with programming rate 5 DEG C/min.It should be noted that dicyanobenzenes absorbing liquid and The GC of dicyanobenzenes measures sample such as modulated: add as interior target diphenyl methane (pure with light in measuring sample 0.1g Medicine Industrial Co., Ltd manufactures, superfine) 0.1g so that it is be dissolved in acetone solvent 10g (Wako Pure Chemical Industries, Ltd. manufactures, Superfine).Hydrogenation generates the GC of liquid and measures sample such as modulated: generating rough after liquid eliminates ammonia from hydrogenation Benzene dimethylamine 0.2g adds as interior target diphenyl methane (Wako Pure Chemical Industries, Ltd.'s manufacture, superfine) 0.1g, make It is dissolved in methanol solvate or dioxane 10g (being Wako Pure Chemical Industries, Ltd.'s manufacture, superfine).
(3) analysis of the moisture concentration in organic facies
Input m-tolunitrile 40g in the pressure vessel (50mL, SUS304 system) defining nitrogen atmosphere, wherein, Using the organic facies collection after liquid-liquid separation or after degassing in enclosed system as sample liquid.After vessel temp is reduced to room temperature, Sample liquid being taken out from container, the determination of trace water device CA-100 type manufactured by Mitsubishi chemical Co., Ltd is dense to moisture Degree is carried out quantitatively.
(4) analysis of the salt in organic facies
(4-1) analysis of carbon acid ion concentration
10 mass % barium chloride solution 8g are put in the pressure vessel (50mL, SUS304 system) defining nitrogen atmosphere With m-tolunitrile 35g, wherein, by the organic facies collection after liquid-liquid separation or after degassing in enclosed system.When will gather The insoluble component generated is filtered by attraction and reclaims, and then this insoluble component is put into beaker, adds 0.1N-in this beaker Hydrochloric acid (Wako Pure Chemical Industries, Ltd.'s manufacture) 10mL, makes insoluble component heating for dissolving.After cooling, by 0.1N-hydroxide Sodium water solution (Wako Pure Chemical Industries, Ltd.'s manufacture) titrates, to carbanion CO3 2-Carry out quantitatively.
(4-2) analysis of ammonium ion concentration
0.1N-dilute sulfuric acid 8g and a methyl is put in the pressure vessel (50mL, SUS304 system) defining nitrogen atmosphere Cyanophenyl 35g, wherein, by the organic facies collection after liquid-liquid separation or after degassing to enclosed system.In this pressure vessel, Organic facies is made fully to dissolve, the aqueous portion classification of sample then will reclaimed from pressure vessel, utilize big electronics strain formula meeting The electrophoretic apparatus that society manufactures is analyzed, thus to ammonium radical ion NH4 +Carry out quantitatively.
＜ embodiment 1 ＞
(ammoxidation operation)
Water (distilled water) 500mL, limit is added in vanadium pentoxide (Wako Pure Chemical Industries, Ltd.'s manufacture, superfine) 229g It is heated to 80～90 DEG C to be stirred limit and be added thereto to oxalic acid (Wako Pure Chemical Industries, Ltd. manufacture, superfine) 477g molten Solve, obtain the solution of vanadium oxalate.It addition, add water 400mL in oxalic acid 963g, being heated to 50～60 DEG C, wherein, limit is abundant Stirring limit is added in water 200mL and there was added chromic anhydride (Wako Pure Chemical Industries, Ltd.'s manufacture, superfine) 252g and obtain Solution also dissolves, and obtains the solution of chromium+oxalic acid.In the solution of gained vanadium oxalate, the solution of chromium+oxalic acid is mixed with 50～60 DEG C, To vanadium-chromium solution.Dissolved phosphorus molybdic acid (Japan's inorganic chemistry industry manufacture, H in water 100mL3(PMo12O40)·20H2O) 41.1g, is added into this vanadium-chromium solution, and then, water 100mL dissolves potassium acetate (Wako Pure Chemical Industries, Ltd. Manufacture, superfine) 4.0g, it is added into wherein, is subsequently added into 20 mass % water silica sols (containing Na2O 0.02 mass %) 2500g, obtains pulp solution.In this pulp solution, add boric acid 78g be sufficiently mixed, carry out heating, concentrate until amount of liquid Become about 3800g, obtain catalyst solution.Use spray dryer, while this inlet temperature to be remained 250 DEG C, outlet temperature Remain 130 DEG C, while this catalyst solution is spray-dried under air circulates, obtain catalyst precursor particles.Use Drying machine, under the air atmosphere of 130 DEG C, is dried this catalyst precursor particles 12 hours, then uses calciner, Roasting 0.5 hour at 400 DEG C, under air circulates, and then, at 550 DEG C, under air circulates, roasting 8 hours, is catalyzed Agent.The atomic ratio of this catalyst is calculated as 1:1:0.5:0.086:0.007:0.009:0.020 with V:Cr:B:Mo:P:Na:K, and this is urged Agent concentration is 50 mass % relative to catalyst gross mass.
Hereinafter, use the manufacture device as the manufacture device shown in Fig. 1, manufacture dicyanobenzenes.At ammoxidation reaction Device A fills the catalyst 6L of above-mentioned preparation, as catalytic bed, uses fluid bed.Using mixing as oxygen supply source air, Meta-xylene is (hreinafter referred to as " MX ".Rhizoma Sparganii gas chemicals) and the gaseous mixture that obtains of ammonia (Rhizoma Sparganii gas chemicals) Body is preheated to 350 DEG C and supplies to this reactor A.For put into condition, MX quantity delivered is set to 350g/h, ammonia/MX mole Than being set to 10, the mol ratio of oxygen/MX is set to 5.4, space velocity GHSV is set to 630h-1.Reaction temperature is set to 420 DEG C, reaction Pressure is set to 0.2MPa.
(1) operation is absorbed
The ammoxidation reaction gas extracted out from the top of ammonia oxidation reactor A is directed into m-dicyanobenzene absorption tower B, by ammonia M-dicyanobenzene in oxidation reaction gas absorbs to m-tolunitrile (Rhizoma Sparganii gas chemicals) solvent.M-dicyanobenzene absorbs Tower B is SUS304 system, is connected with the pipe arrangement of aerofluxus at top, is set to following structure: main part is internal diameter 100mm Φ, highly 800mm, and the region of length 450mm of main part bottom can carry out steam heating with the form of dual pipe, is provided with in bottom The mouth blown of supply ammoxidation reaction gas.This absorption tower B receives m-tolunitrile 2kg, remains 140 DEG C, by above-mentioned ammonia Oxidation reaction gas is sent into the flow of 353g/ hour from above-mentioned mouth blown, thus first between this ammoxidation reaction gas is passed through Base cyanophenyl absorbs 2 hours.It should be noted that the pipe arrangement of aerofluxus is provided with pressure regulator valve, become one with the pressure in the B of absorption tower Fixed mode is controlled.Ammoxidation reaction gas is 1～2 second with the time of contact of m-tolunitrile.At the end of absorption two Moisture concentration in cyano group benzene (m-dicyanobenzene) absorbing liquid is 0.16 mass %, and carbon acid ion concentration is 108 mass ppm, ammonium Ion concentration is 1203 mass ppm.It addition, the consisting of of this m-dicyanobenzene absorbing liquid: m-dicyanobenzene 24.98 mass %, Methyl cyanophenyl 73.89 mass %, 3-cyanobenzamide 0.467 mass %, 3-cyanobenzoic acid 0.156 mass %.
(2) abstraction process
M-dicyanobenzene absorbing liquid 235g is put into mixing channel C thus forms full liquid status, liquid temperature is adjusted to 100 DEG C. Mixing channel C uses the autoclave of band having heaters and blender, and (SUS304 system, volume 250mL, top possess and are set as The counterbalance valve of 0.5MPaG, bottom possess nozzle).While m-dicyanobenzene absorbing liquid stirring limit is warming up to the temperature of regulation, the most temporarily Time stop stirring.Then, 25% ammonia (Wako Pure Chemical Industries, Ltd.'s manufacture, superfine) will be dissolved with in pure water 34.06g 1.58g and ammonium carbonate (Wako Pure Chemical Industries, Ltd. manufacture, superfine) 3.96g and the alkaline aqueous solution 39.6g for preparing are from mixed The bottom nozzle closing groove C supplies with the speed of 5g/ minute, in order to the pressure in mixing channel C being remained 0.5MPaG, extract out from The m-dicyanobenzene absorbing liquid that the counterbalance valve on top overflows.In mixing channel, the m-dicyanobenzene absorbing liquid of residual is 198g.Afterwards, again Start stirring, liquid temperature is adjusted to 100 DEG C, keep 10 minutes under the stirring of 1000rpm.
(3) liquid-liquid separation operation
Stop the stirring in mixing channel C, the mixed liquor limit of m-dicyanobenzene absorbing liquid and alkaline aqueous solution is remained liquid temperature The state limit of 100 DEG C stands 10 minutes, is separated into organic facies (upper strata) and aqueous phase (lower floor).I.e., it is also possible to using mixing channel C as Liquid-liquid separation groove D uses.Afterwards, by with the alkaline aqueous solution of material same composition of preparation in abstraction process from mixing channel C's Bottom nozzle supplies with the speed of 2g/ minute, extracts the organic facies after liquid-liquid separation continuously out by the counterbalance valve on top 120g.The moisture concentration of the organic facies of this extraction is 3.04 mass %, and carbon acid ion concentration is 2223 mass ppm, ammonium root from Sub-concentration is 1312 mass ppm, and ammonium carbonate salts concentration is 3556 mass ppm.It addition, the consisting of of this organic facies: m-dicyanobenzene 24.26 mass %, m-tolunitrile 71.73 mass %, 3-cyanobenzamide 0.454 mass %, 3-cyanobenzoic acid 0.011 Quality %.
(4) degassing process
The organic facies extracted out from liquid-liquid separation groove D is directly fed to the degassing tower E of continuous way.Organic facies by supply Temperature be set to 140 DEG C, feed speed be set to 2g/ minute.Column bottom temperature is set to the temperature of supply as mutually synthermal, tower top pressure Power is set to 101.3kPa.Carbon dioxide and ammonia that salt decomposes and generates are discharged from the tower top of degassing tower E.It addition, will be with titanium dioxide Water and organic solvent that carbon is discharged from tower top together with ammonia reclaim, and do not make water and organic solvent the most all be back to degassing tower E.Being 3.01 mass % by the moisture concentration of the organic facies obtained at the bottom of tower, carbon acid ion concentration is 51 mass ppm, ammonium radical ion Concentration is 151 mass ppm, and ammonium carbonate salts concentration is 81 mass ppm.It addition, the consisting of of this organic facies: m-dicyanobenzene 24.35 Quality %, m-tolunitrile 72.00 mass %, 3-cyanobenzamide 0.455 mass %, 3-cyanobenzoic acid 0.011 matter Amount %.
(5) low boiling separation circuit
To be directly fed to the distillation column the lowest boiling knockout tower F's of continuous way from the organic facies extracted out at the bottom of the tower of degassing tower E Stage casing.The temperature of the organic facies of supply is set to the column bottom temperature of previous operation as mutually synthermal, and feed speed is set to 2g/ and divides Clock.For the condition of low boiling knockout tower F, tower top pressure is set to 5kPa, tower top temperature be set to 120 DEG C, column bottom temperature be set to 180 DEG C, at the bottom of tower in holdup time be set to 20 minutes.By m-tolunitrile with other low-boiling compounds from the tower of low boiling knockout tower F Top is removed, and the organic facies using the m-dicyanobenzene of molten state as main component is extracted out from the bottom of tower simultaneously.By having of obtaining at the bottom of tower Consisting of of machine phase: m-dicyanobenzene 97.39 mass %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 1.821 matter Amount %, 3-cyanobenzoic acid 0.043 mass %.
＜ embodiment 2 ＞
(6) hydrogenation process
At 2MPa, under conditions of 25 DEG C, in dissolving tank G (SUS304 system), make molten state to obtain in embodiment 1 M-dicyanobenzene is dissolved in the liquid ammonia of 9 mass parts as organic facies 1 mass parts of main component.Then, from the end of dissolving tank G The solution comprising insoluble component is extracted in portion out, uses sintered metal filter (aperture 40 μm, stainless steel) as filter H, leads to Cross and utilize the liquid conveying of pressure differential to filter, obtain the hydrogenated raw material liquid comprising m-dicyanobenzene.
The hydrogenation reactor I (SUS304 system, internal diameter 13mm φ) of pipe vertical type fills nickel content 50 mass % The catalyst of size is pulverized and be have adjusted to the most commercially available carrier band nickel/kieselguhr catalyst (cylindric, diameter 3mm Φ, highly 3mm) (12-22mesh (mesh)/JIS standard) 25.0g, under hydrogen gas stream, carries out reduction at 200 DEG C and makes its activation.After cooling, In reactor I, it is pressed into hydrogen gas, remains the certain pressure of 8MPa, by from outside heating, by catalyst layer Temperature maintains 80 DEG C.From reactor I top, the flow velocity with 18NL/ hour supplies hydrogen gas and makes it circulate, simultaneously by upper State hydrogenated raw material liquid to continuously feed with the speed of 25.0g/ hour from reactor top.Hydrogenated raw material liquid and hydrogen are by catalysis Oxidant layer, removes ammonia from the hydrogenation liquid obtained by reactor lower part, obtains rough m-xylene diamine.Gained rough isophthalic diformazan Consisting of of amine: m-xylene diamine 91.16 mass %, 3-methyl-benzyl amine 0.10 mass %, is not detected by m-dicyanobenzene.Residue The oligomeric species that composition is m-xylene diamine, the high boiling polymer that be can't detect by gas chromatography.
＜ embodiment 3 ＞
For the water discharged from the tower top of degassing tower E in (4) degassing process and organic solvent, water and organic solvent are divided From, only organic solvent is back to degassing process, in addition, manufactures dicyano with condition similarly to Example 1 and operation Benzene.
In degassing process, the moisture concentration of the organic facies obtained at the bottom of the tower of degassing tower E be 0.99 mass %, carbonate from Sub-concentration is 51 mass ppm, and ammonium ion concentration is 151 mass ppm, and ammonium carbonate salts concentration is 81 mass ppm.It addition, this has Consisting of of machine phase: m-dicyanobenzene 24.86 mass %, m-tolunitrile 73.50 mass %, 3-cyanobenzamide 0.465 matter Amount %, 3-cyanobenzoic acid 0.011 mass %.
In low boiling separation circuit, by consisting of of the organic facies obtained at the bottom of the tower of low boiling knockout tower F: m-dicyanobenzene 97.42 Quality %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 1.844 mass %, 3-cyanobenzoic acid 0.039 matter Amount %.Compared with Example 1, m-dicyanobenzene concentration is equal extent.
＜ embodiment 4 ＞
By the m-dicyanobenzene of molten state that obtains in embodiment 3 as main component organic facies with embodiment 2 The same method of hydrogenation process hydrogenates.Consisting of of the rough m-xylene diamine of gained: m-xylene diamine 91.18 mass %, 3-methyl-benzyl amine 0.10 mass %, is not detected by m-dicyanobenzene.Remaining composition is the oligomeric species of m-xylene diamine, passes through The high boiling polymer that gas chromatography can't detect.Compared with Example 2, m-xylene diamine concentration is equal extent.
＜ embodiment 5 ＞
(3) liquid-liquid separation operation will obtain and supply at the bottom of the temperature of the organic facies to degassing tower E and the tower of degassing tower E Temperature is set to 180 DEG C, in addition, manufactures dicyanobenzenes with condition similarly to Example 1 and operation.
In degassing process, the moisture concentration of the organic facies obtained at the bottom of the tower of degassing tower E be 2.98 mass %, carbonate from Sub-concentration is 25 mass ppm, and ammonium ion concentration is 75 mass ppm, and ammonium carbonate salts concentration is 41 mass ppm.It addition, this is organic Consisting of of phase: m-dicyanobenzene 24.36 mass %, m-tolunitrile 72.03 mass %, 3-cyanobenzamide 0.455 matter Amount %, 3-cyanobenzoic acid 0.011 mass %.
In low boiling separation circuit, by consisting of of the organic facies obtained at the bottom of the tower of low boiling knockout tower F: m-dicyanobenzene 97.30 Quality %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 1.920 mass %, 3-cyanobenzoic acid 0.040 matter Amount %.Compared with Example 1, m-dicyanobenzene concentration slightly reduces.
＜ embodiment 6 ＞
The m-dicyanobenzene of the molten state obtained in embodiment 5 is utilized and embodiment 2 as the organic facies of main component The same method of hydrogenation process hydrogenate.Consisting of of the rough m-xylene diamine of gained: m-xylene diamine 91.07 matter Amount %, 3-methyl-benzyl amine 0.10 mass %, is not detected by m-dicyanobenzene.Remaining composition is the oligomer of m-xylene diamine Class, the high boiling polymer that be can't detect by gas chromatography.Compared with Example 2, m-xylene diamine concentration slightly reduces.
＜ embodiment 7 ＞
(3) liquid-liquid separation operation will obtain and supply at the bottom of the temperature of the organic facies to degassing tower E and the tower of degassing tower E Temperature is set to 180 DEG C, for the water discharged from the tower top of degassing tower E in (4) degassing process and organic solvent, by water and organic molten Agent separates, and only organic solvent is back to degassing process, in addition, with condition similarly to Example 1 and operation manufacture two Cyano group benzene.
In degassing process, the moisture concentration of the organic facies obtained at the bottom of the tower of degassing tower E be 0.26 mass %, carbonate from Sub-concentration is 25 mass ppm, and ammonium ion concentration is 75 mass ppm, and ammonium carbonate salts concentration is 41 mass ppm.It addition, this is organic Consisting of of phase: m-dicyanobenzene 25.04 mass %, m-tolunitrile 74.05 mass %, 3-cyanobenzamide 0.468 matter Amount %, 3-cyanobenzoic acid 0.011 mass %.
In low boiling separation circuit, by consisting of of the organic facies obtained at the bottom of the tower of low boiling knockout tower F: m-dicyanobenzene 97.43 Quality %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 1.839 mass %, 3-cyanobenzoic acid 0.038 matter Amount %.Compared with Example 1, m-dicyanobenzene concentration is equal extent.
＜ embodiment 8 ＞
The m-dicyanobenzene of the molten state obtained in embodiment 7 is utilized and embodiment 2 as the organic facies of main component The same method of hydrogenation process hydrogenate.Consisting of of the rough m-xylene diamine of gained: m-xylene diamine 91.19 matter Amount %, 3-methyl-benzyl amine 0.10 mass %, is not detected by m-dicyanobenzene.Remaining composition is the oligomer of m-xylene diamine Class, the high boiling polymer that be can't detect by gas chromatography.Compared with Example 2, m-xylene diamine concentration is equal Degree.
＜ comparative example 1 ＞
Omit (4) degassing process, the organic facies obtained in (3) liquid-liquid separation operation is directly fed to low boiling knockout tower F, in addition, manufactures dicyanobenzenes with condition similarly to Example 1 and operation.It should be noted that supply to low boiling divides Temperature from the organic facies of tower F is 140 DEG C, feed speed is 2g/ minute, is set to condition similarly to Example 1.
By the m-dicyanobenzene of the molten state obtained at the bottom of the tower of low boiling knockout tower F as main component in low boiling separation circuit The consisting of of organic facies: m-dicyanobenzene 97.20 mass %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 2.017 Quality %, 3-cyanobenzoic acid 0.043 mass %.Compared with Example 1, m-dicyanobenzene concentration reduces by 0.19 mass %, it is seen that Going bad to m-dicyanobenzene.It addition, compared with Example 1,3-cyanobenzamide increases.
Consisting of of the rough m-xylene diamine obtained through hydrogenation process similarly to Example 2: m-xylene diamine 90.98 mass %, 3-methyl-benzyl amine 0.10 mass %, be not detected by m-dicyanobenzene.Remaining composition is m-xylene diamine Oligomeric species, the high boiling polymer that be can't detect by gas chromatography.Compared with Example 2, m-xylene diamine concentration Reduce by 0.18 mass %.
＜ comparative example 2 ＞
The temperature of organic facies obtained in (3) liquid-liquid separation operation and supply to low boiling knockout tower F is set to 180 DEG C, removes Outside this, manufacture dicyanobenzenes with the condition as comparative example 1 and operation.
By the m-dicyanobenzene of the molten state obtained at the bottom of the tower of low boiling knockout tower F as main component in low boiling separation circuit The consisting of of organic facies: m-dicyanobenzene 96.97 mass %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 2.249 Quality %, 3-cyanobenzoic acid 0.040 mass %.Compared with Example 1, m-dicyanobenzene concentration reduces by 0.42 mass %, it is seen that Going bad to m-dicyanobenzene.It addition, compared with Example 1,3-cyanobenzamide increases.
Consisting of of the rough m-xylene diamine obtained through hydrogenation process similarly to Example 2: m-xylene diamine 90.78 mass %, 3-methyl-benzyl amine 0.10 mass %, be not detected by m-dicyanobenzene.Remaining composition is m-xylene diamine Oligomeric species, the high boiling polymer that be can't detect by gas chromatography.Compared with Example 2, m-xylene diamine concentration Reduce by 0.38 mass %.
＜ comparative example 3 ＞
Tower top pressure in (4) degassing process is changed to 311.3kPa, in addition, with bar similarly to Example 1 Part and operation manufacture dicyanobenzenes.
In degassing process, the moisture concentration of the organic facies obtained at the bottom of the tower of degassing tower E be 3.01 mass %, carbonate from Sub-concentration is 1673 mass ppm, and ammonium ion concentration is 874 mass ppm, and ammonium carbonate salts concentration is 2677 mass ppm.It addition, Consisting of of this organic facies: m-dicyanobenzene 24.29 mass %, m-tolunitrile 71.83 mass %, 3-cyanobenzamide 0.490 mass %, 3-cyanobenzoic acid 0.011 mass %.Compared with Example 1, ammonium carbonate salts concentration increases.
In low boiling separation circuit, by consisting of of the organic facies obtained at the bottom of the tower of low boiling knockout tower F: m-dicyanobenzene 97.26 Quality %, m-tolunitrile 0.10 mass %, 3-cyanobenzamide 1.960 mass %, 3-cyanobenzoic acid 0.043 matter Amount %.Compared with Example 1, m-dicyanobenzene concentration reduces by 0.13 mass %, it is seen that going bad of m-dicyanobenzene.It addition, with reality Executing example 1 to compare, 3-cyanobenzamide increases.
Consisting of of the rough m-xylene diamine obtained through hydrogenation process similarly to Example 2: m-xylene diamine 91.03 mass %, 3-methyl-benzyl amine 0.10 mass %, be not detected by m-dicyanobenzene.Remaining composition is m-xylene diamine Oligomeric species, the high boiling polymer that be can't detect by gas chromatography.Compared with Example 2, m-xylene diamine concentration Reduce by 0.13 mass %.
Its content, based on Japanese patent application (Patent 2014-046426) filed in 10 days March in 2014, is made by the application For with reference to introducing wherein.
Industrial applicability
Dicyanobenzenes is effective as pesticide, functional material.Especially as the raw material of pesticide, polyamide, The intermediate raw materials such as firming agent are useful compounds.It addition, benzene dimethylamine is at resin curing agent, nylon, polyurethane, rubber medicine Product, paper conversion agent, the wide scope of fibre finish industrial circle in be useful compound.
Description of reference numerals
A: ammonia oxidation reactor, B: m-dicyanobenzene absorption tower, C: mixing channel, D: liquid-liquid separation groove, E: degassing tower, F: low Boiling knockout tower, G: dissolving tank, H: filter, I: hydrogenation reactor.

Claims (10)

1. a manufacture method for dicyanobenzenes, it possesses following operation:
(1) absorb operation, make ammoxidation reaction gas and the organic solvent exposure of dimethylbenzene, make dicyanobenzenes be dissolved in described in have Machine solvent and obtain dicyanobenzenes absorbing liquid, the ammoxidation reaction gas of described dimethylbenzene contain make dimethylbenzene carry out ammoxidation and The dicyanobenzenes obtained；
(2) abstraction process, makes described dicyanobenzenes absorbing liquid and comprises the free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline group The alkaline aqueous solution contact of the salt of more than a kind in the group become, by by the carboxylic acid in described dicyanobenzenes absorbing liquid and described alkali Property aqueous solution in alkali neutralize reaction generate water soluble salt extract to aqueous phase；
(3) liquid-liquid separation operation, makes through the described dicyanobenzenes absorbing liquid of described abstraction process and described alkaline aqueous solution Mixed liquor is separated into organic facies and aqueous phase；
(4) degassing process, by the free ammonium carbonate of choosing contained in the described organic facies of described liquid-liquid separation operation, carbonic acid The salt of more than a kind in the group of hydrogen ammonium and aminoquinoxaline composition decomposes, and is separated by described salt from described organic facies；With,
(5) low boiling separation circuit, distills the described organic facies through described degassing process, by tool contained in described organic facies The composition having the boiling point lower than described dicyanobenzenes separates from described organic facies, obtains described dicyanobenzenes.
Manufacture method the most according to claim 1, wherein, the pressure of the gas phase in described degassing process be 101.3kPa with Under.
Manufacture method the most according to claim 1 and 2, wherein, the temperature of the liquid phase in described degassing process is 70～180 ℃。
4., according to the manufacture method according to any one of claims 1 to 3, wherein, in described abstraction process, described alkali is relative The ammonia of the molal quantity that total mole number is 1～50 times of described carboxylic acid contained in described dicyanobenzenes absorbing liquid.
5., according to the manufacture method according to any one of Claims 1 to 4, wherein, in described abstraction process, make described alkaline water Solution and described dicyanobenzenes absorbing liquid contact under the temperature conditions below 140 DEG C.
6. according to the manufacture method according to any one of Claims 1 to 5, wherein, described dimethylbenzene is meta-xylene, described two Cyano group benzene is m-dicyanobenzene.
7. the catalysis according to the manufacture method according to any one of claim 1～6, wherein, used in described ammoxidation reaction Agent is the catalyst containing vanadium and/or chromium.
8. according to the manufacture method according to any one of claim 1～7, wherein, described absorption operation absorbs described dicyan The described organic solvent of base benzene is for selecting free alkylbenzene, heterocyclic compound, aromatic nitrile compound and heterocyclic nitrile compounds composition Group in the organic solvent of more than a kind.
9. one kind is manufactured benzene dimethylamine by the dicyanobenzenes obtained by the manufacture method according to any one of claim 1～8 Method, it possesses following hydrogenation process: make described dicyanobenzenes be dissolved in solvent, the most in the presence of a catalyst, at liquid Hydrogenate in mutually.
10. a manufacture device for dicyanobenzenes, it possesses such as lower unit:
(1) absorptive unit, makes ammoxidation reaction gas and the organic solvent exposure of dimethylbenzene, make dicyanobenzenes be dissolved in described in have Machine solvent and obtain dicyanobenzenes absorbing liquid, the ammoxidation reaction gas of described dimethylbenzene contain make dimethylbenzene carry out ammoxidation and The dicyanobenzenes obtained；
(2) extraction unit, makes described dicyanobenzenes absorbing liquid and comprises the free ammonium carbonate of choosing, ammonium hydrogen carbonate and aminoquinoxaline group The alkaline aqueous solution contact of the salt of more than a kind in the group become, by by the carboxylic acid in described dicyanobenzenes absorbing liquid and described alkali Property aqueous solution in alkali neutralize reaction generate water soluble salt extract to aqueous phase；
(3) liquid-liquid separation unit, makes the described dicyanobenzenes absorbing liquid sent from described extraction unit and described alkaline aqueous solution Mixed liquor be separated into organic facies and aqueous phase；
(4) degassing unit, by the free ammonium carbonate of choosing contained from the described organic facies that described liquid-liquid separation unit is sent, carbon The salt of more than a kind in the group of acid hydrogen ammonium and aminoquinoxaline composition decomposes, and is separated by described salt from described organic facies；With,
(5) low boiling separative element, the described organic facies will sent from described degassing unit distillation, by contained in described organic facies The composition with the boiling point lower than described dicyanobenzenes separates from described organic facies, obtains described dicyanobenzenes.
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